Halogen-carboxylic acid esters



Patented Jan. 31, 1939 2,145,443

UNITED STATES PATENT OFFICE HALOGEN-CARBOXYLIC ACID ESTEBS Benjamin R.Harris, Chicago, Ill.

No Drawing. Original application January 21,

1937, Serial No. 121,563. Divided and this application April 24, 1937,Serial No. 138,839

11 Claims. (CL 260-487) My invention relates to a new class ofchemcumstances the compounds may contain more. ical substances, and morein particular to a new than one halogen-containing mono-carboxylic orclass of'chemical substances, particularly adapted fatty acid group, butin all cases there must be for use as intermediates for the preparationof at least one such group. The halogen-containing detergents,penetrating, lathering, flotation and mono-carboxylic or fatty acidradical isof relanti-spattering agents, and for frothing puratively lowmolecular weight and should contain poses. not more than eight carbons.

In certain classes of industries, there is a Considering the compoundsfrom another asneed for a certain class of chemical substances p t. he me in each y 0011118111 at least w usually used in relatively smallquantities but one relat y high molecular Weight pop m capable of use inlarger quantities to secure an group and at least one relatively lowmolecular effect principally the result of a wetting action' We t o e ona n up W in t such as at a water-oil interface. In the textile class ofcompounds to which my present invenand dyeing industries, for examplethere are tion relates, are mono-carboxylic acid radicals.

15 many situations where a wetting or detergent A more ompleteunderstanding of what m y 15 action is imperative and many differentchemicomprise the lipophile group n h p c l cal substances have beenproduced calculated to character of the halogen-co a oreduce surfacetension and promote wetting in boxylic acid group will be had as thedetailed these industries. The use of prior art substances e pti n P c ccs.

W has not been attended with unqualified success More specifically, thesubstances of my invenin all instances. In certain other types of intionare lower molecular weight halo en-condustries, such as the margarineindustries, for tam n m r y or at y d st s f example, problems inpreventing the spattering p d xy s st n at ast one yd y of margarine infrying have arisen. These probgroup of the polyhy y S s a e being c lemsare considered by some investigators as enfied with a carboxylic acidcontaining at least tirely a matter of wetting; in other words. by fourcarbon atoms d ab y between ei ht promoting greater attraction betweenthe oleagiand eighteen carbon atoms. Examples of comnous and aqueousportions of the emulsion pounds falling within the scope of my inventionat the interfaces thereof. Although the problem are as follows:

M is probably not one of wetting action entirely,

it appears that certain compounds which in theory tend to concentrate atthe water-oil interface have an eifect upon the spattering behavior ofmargarine. This problem is. discussed and a remedy disclosed in myPatent No. 1,917,256, filed as a continuation-in-part of a priorapplication, Oetylether olmon s e rin ehlor eetate Serial No. 475,622,now Patent No. 1,917,250.

The principal object of my invention is the QH,-O g-C H provision of anew class of chemical substances mm which are in general of relativelysimple structure and can be cheaply made in'commercial quantities.

Still another object of my invention is the la r n lor etm provision ofa class of intermediate chemical 0 compounds from which the chemicalsubstances oH,0tt--cuHn discussed above may be produced.

Other objects and features of the invention will be apparent from aconsideration of the fol- HFO C CH OHT'CH lowing detailed description. 1

The substances of my invention are in gen-= Mmwmfln gmwbumm eralesterderivatives of lower molecular weight g halogen-containingmono-carboxylic 'or fatty CHPO acids wherein the group esterified withthe said nr-o-c-0n-o1 halogen-containing acid has a lipophile radical Iwith at least four carbon atoms. In certain cir- Monopalmitic ester oiethylene glycol chlorpropionate Di-cliloracetic acid ester oi mono'olelnMono-palmitic acid ester oi tri-methyleng glycol chioracetateHa-O-C-CILCI csteoric, 8-benzoic, c'cliloracetic acid ester of glycerinMonostearic acid ester of diatliylenc glycol chloracetatc Mono-oleicacid ester of dicthylene glycol chloracetatc Generally speaking, I mayselect many diflerent types of compounds as lipophile groups which areto be sterifled with the polyhydroxy substances, principally compoundshaving lipophile radicals of relatively high molecular weight. Forexample, the following materials may be uti-- lized as sources oflipophile groups: hydroaromatic acids such as naphthenic acid, abieticacid, hydroxy aromatic acids such as hydroxy benzoic acid, fatty acidssuch as butyric acid, caprylic acid, caproic acid, oapric acid,saturated and unsaturated higher aliphatic acids such as the higherfatty acids containing at least eight carbon atoms and including'melissic acid, stearic acid, oleic acid, ricinoleic acid, linoleicacid, laurlc acid, mvristic acid, palmitic acid, mixed higher fattyacids, derived from animal or vegetable sources, for example, lard,coconut oilQsesame oil, corn oil, cottonseed'oil, sardine oil, partiallyor completely hydrogenated animal and vegetable oils such as thosementioned, fatty acids derived from various waxes such as beeswax,spermaceti, and carnauba wax and carboxyllc acids derived, by oxidationand other methods, from petroleum.

The polyhydroxy substances which provide the linkage between thelipophile group and the sulpho-carboxylic group may be selected from alarge class and include glycerol; glycol such as ethylene glycol,propylene glycol, trimethylene glycol, butylene glycol and the like;polyglycols such as 'diethylene glycol; polyglycerols such asdiglycerol, triglycerol, tetraglycerol and the like including mixturesthereof; sugars such as dextrose, sucrose, xylose, galactose, fructose,maltose, mannose and the like; sugar alcohols such as arabitol,mannitol, sorbitol and dulcitol; and 'polyhydroxy-carboxylic acids suchas tartaric acid, mucic acid, saccharic acid, gluconic acid, glucuronicacid, gulonic acid, mannonic acid, trihydroxyglutaric acid, glycericacid, carboxylic oxidation products of polyglycerols, others of similarcharacter, and hydroxyethyl and hydroxypropyl ether derivatives of theabove, as for example:

(For convenience all hydroxyl groups are writ ten facing one way.)

The compounds of my invention are produced by reacting one or more freeor esteriflable by; droxy groups of a polyhydroxy substance orderivative of a polyhydroxy substance with a halogeno-carborxylic acidsuch as chloracetic or bromacetic acid, or with a halogeno-carboxyllcacid halide such as chlor-acetyl chloride or bromacetyl bromide, to forma chloracetate or bromacetate.

700 parts of monostearine were heated with 1'75 parts of chloracetlcacid for 3 hours at a temperature of 150-160 degrees C. in an atmosphereof CO2 and with product was washed free of chloracetic acid with 4 timesits own volume of water at degrees C.

and, to assist in separation, parts 01' salt were added to the wash.water.

' ExAM 1 Lr: TI

Monostearin chloracetate 100 parts of monostearine were heated with 60.parts of chloracetlc acid at degrees C. for several hours, using astream of CO2 for the agitation. The reaction purpose of agitation andto remove water coming off in the reaction, The heating was continueduntil the chlorine content corresponded approximately at monostearinechloracetate. When the reaction was completed, the product was washedfree of chloracetic acid and dried.

EXAMPLEIII 'Distearine chloracetate 200 parts parts of chloracetic acidfor 3 hours at -170 degrees C. When the reaction was completed theproduct was washed free of chloracetic acid and dried.

EXAMPLE IV M cmostearz'ne clichlo racetate 500 parts of monostearinewere heated with 500 parts of chloracetic acid at a temperature of 160degrees C. for several hours using a stream of CO2 for the purpose ofagitation and to remove water of reaction. The heating was continueduntil the chlorine content corresponded to approximately 100% ofmonostearine dichloracetate.

Erna V Monostearz'c acid ester of methylene glycol chlomcetate 500 partsof diethylene glycol monostearate, prepared by heating a mixture of onepart of stearic acid with one part of diethylene glycol at a temperatureof about 220 degrees C., using 0.1% KOH until the free fatty acidcontent is down to about A; to 1%, were heated with 250 parts ofchloracetic acid at 160-170 degrees C. for 4 hours. The product waswashed free of chloracetic acid and dried.

EXAMPLE VI Cottonseed oil glycol chloracetate 500 parts of cottonseedoil fatty acid mono esters of diethylene glycol, prepared byreesterifying cottonseed oil with diethylene glycol, were heated with250 parts of chloracetic acid for 3 hours at 160-170 degrees C. in anatmosphere of C02.

EXAMPLE Coconut mono fatty acid esters of diethylene glycol chlomcetate400 parts of the fatty acid mono esters of diethylene glycol with mixedcoconut oil fatty acids were heated with 260 parts of chloracetic acidfor 3 hours at 160 degrees C. using a streamv of CO2 for agitation andremoval of moisture.

- EXAMPLE VIE Monococonut oil fatty acid ester of ylycerinech-lm'acetate Coconut oil mono-fatty acid ester of glycerinewas'prepared'by reesterlfying coconut oil with excess of glycerine andremoving the excess of glycerine. 300 parts of said ester were heatedwith 200 parts of chloracetic acid at 160 degrees C. for several hoursin an atmosphere of CO2 until the theoretical chlorine contentcorresponding to the mbnochloracetate was obtained.

Thecompounds of'my invention may be represented by the following generalformula of distearine were heated with 65 fatty acid esters ofdiethyiene wherein R'is the residue .of a polyhydroxy substance in whichthe hydrogen of at least one hydroxyl group is substituted by an acyl'group containing at least four carbon atoms and preferably betweeneight and eighteen carbon atoms,

'1! is the carbon-hydrogen residue of the halogeno-carboxylic acid, M ishalogen, and w is a small whole number, at least one.

. It is apparent, in the light of the above examples, that the lipophilegroup "may in itself contain hydrophile radicals. For example, in thecase of monostearin chloracetate, the hydroxy radical of the secondglycerine carbon has 'a recognized hydrophillic character. The group asa whole, however, of which this hydroxy radical is a part, is dominantlylipophile, the single hydroxy radical in such a compound beinginsuflicient to impart dominant hydrophile characteristics to the groupas a whole. When the character" R is used in the formula, therefore, torepresent a lipophile group, it is with the assumption that the group asa whole does not possess a hydrophillic character.

Considering more specifically the character of the lipophile group, itwill at once be apparent that for the most part I employ esters ofglycerol,

glycols or other polyhydric alcohols or polyhy droxy substances attachedto the halogen-containing mono-carboxylic or fatty acid of relativelylow molecular weight through .an ester linkage. In so far as thehalogen-containing mono-carboxylic or fatty acid group is concerned, Imay employ a chlor-acetate, chlor-butyrate, or other similar groupscontaining, generally, not more than eight carbon atoms. In general,however, I have found that the chlor-or brom-acetates particularlyproduce compounds of exceptionally desirable characteristics and theyhave the advantage of being relatively inexpensively produced fromcommercially available substances.

The term residue, as used throughout the specification and claims, isemployed in its ordinarily understood chemical significance. Forexample, where one of the hydroxyl groups of glycerine is esterifiedwith a fatty acid and another of the hydroxyl groups of the glycerine isester-' ified with a halogen-containing mono-carboxylic acid, that whichremains of the glycerine molecule, for exple is the "residue of thepolyhydroxy substance, in this case glycerine.

Similarly, the term "carbon-hydrogen residue of ahalogen-containingmono-carbo-xylic acid is employed as in conventionalchemical nomenclaacid esters therein disclosed may be prepared.

It is obvious, of course, that said intermediates may be employed in thepreparation of other types of compounds and may possess utility as suchin various arts and industries.

What I claim as new and desire to protect by Letters Patent of theUnited States is:

1. Esters of polyhydroxy substances wherein at least one hydroxy groupof said polyhydroxy. substances is esterifled with a fatty acidcontaining at least eight carbon atoms and at least one hydroxy group ofsaid polyhydroxy substances is esterifled with a halogen-containingmonocarboxyllc acid having less than eight carbon atoms. 1

2. Esters of fatty acid monoglycerides, the fatty acid radical of whichcontains at least eight carbon atoms,- at least one hydroxy group ofsaid monoglycerides being esterified with a halogencontainingmonocarboxylic acid having less than eight carbon atoms.

3. A halogen-containing aliphatic mono-carboxylic acid ester of a memberof the group consisting of fatty acid monoglycerides, fatty aciddiglycerides, and mixtures thereof, said halogen-containing aliphaticmono-carboxyiic acid having less than eight carbon atoms, and theradicals of said fatty acids containing at least eight carbon atoms.

4. Chloracetates of a member of the group consisting of fatty acidmonoglycerides, fatty acid diglycerides, and mixtures thereof, theradicals of said fatty acids containing at least eight carbon atoms.

5. Bromacetates of a member of the group consisting of fatty acidmonoglycerides, fatty acid diglycerides, and mixtures thereof, theradicals of said fatty acids containing at least eight carbon atoms.

6. A halogen-containing aliphatic monocarboxylic acid ester ofmonostearln, the radical of said halogen-containing aliphaticmono-carboxylic acid having less than eight carbon atoms.

'7. Chemical compounds f the class consisting the radical of one.

of monostearln chloracetate and monostearln bromoacetate.

8. A chemical compound corresponding to the wherein R 'is the residue ofa polyhydroxy subhydroxy substance is a member of the group consistingof glycols, glycerol, polyglycols, polyglycerols, sugars, and sugaralcohols.

10. A chemical compound corresponding to the general formula n-o-o-ommwherein R is the residue of a polyhydroxysubstance in which the hydrogenof at least one hydroxyl group is substituted by an acyl groupcontaining at ieastfour carbon atoms, and M is halogen.-

11. A chemical compound corresponding to the formula R O C XM wherein Ris the residue of a polyhydrox'y substance in which the hydrogen of atleast one hydroxyl group is substituted by an acyl group containing atleast four carbon atoms, X is the carbon-hydrogenresidue of ahalogeno-carboxylic acid containing less than eight carbon atoms, M ishalogen, and w is a small whole number, at least BENJAMIN R. HARRIS.

